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Related Concept Videos

Properties of Organometallic Compounds01:23

Properties of Organometallic Compounds

Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
Structural Isomerism02:34

Structural Isomerism

Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH301:11

ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3

All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
Coordination Number and Geometry02:57

Coordination Number and Geometry

For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
Aromatic Hydrocarbon Cations: Structural Overview01:18

Aromatic Hydrocarbon Cations: Structural Overview

Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group with both...
Aromatic Hydrocarbon Anions: Structural Overview01:18

Aromatic Hydrocarbon Anions: Structural Overview

Neutral hydrocarbons like cyclopentadiene with an odd number of carbon atoms and one intervening CH2 group in the ring are not aromatic. Cyclopentadiene with 4 π electrons does not satisfy the 4n + 2 π electron rule. Additionally, the intervening CH2 group is sp3 hybridized and lacks a vacant p orbital, thereby interrupting the overlap of p orbitals in a continuous manner and preventing the delocalization of π electrons throughout the ring.
Due to the absence of continuous overlap of p...

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Discovery and Synthesis Optimization of Isoreticular Al(III) Phosphonate-Based Metal-Organic Framework Compounds Using High-Throughput Methods
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Structures and reactivity patterns of group 9 metallocorroles.

Joshua H Palmer1, Atif Mahammed, Kyle M Lancaster

  • 1Beckman Institute, California Institute of Technology, Pasadena, California 91125, USA.

Inorganic Chemistry
|September 10, 2009
PubMed
Summary
This summary is machine-generated.

This study characterizes Group 9 metallocorroles, revealing structural and electronic differences between cobalt, rhodium, and iridium complexes. Ligand affinities increase down the group, with surprising invariance in reduction potentials.

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Metallocorroles are macrocyclic ligands with diverse applications in catalysis and medicine.
  • Understanding the electronic and structural properties of Group 9 metallocorroles is crucial for designing new functional materials.

Purpose of the Study:

  • To fully characterize Group 9 metallocorroles (Co, Rh, Ir) with tris-pentafluorophenyl substituents.
  • To investigate the impact of metal identity and axial ligands on structural, spectroscopic, and electrochemical properties.

Main Methods:

  • Single-crystal X-ray diffraction for structural analysis.
  • Spectroscopic techniques (e.g., EPR) for electronic structure determination.
  • Electrochemical methods (e.g., cyclic voltammetry) for redox potential measurements.

Main Results:

  • Crystal structures show increasing metal-N bond lengths from Co to Rh/Ir.
  • Ligand affinities for axial coordination sites increase significantly in the order Co < Rh < Ir.
  • Reduction potentials exhibit surprising invariance across different metal centers and coordination numbers.
  • Electron paramagnetic resonance (EPR) spectroscopy reveals corrole-centered oxidation for Co/Rh and metal-centered oxidation for Ir complexes.

Conclusions:

  • The electronic and structural properties of Group 9 metallocorroles are tunable by metal identity and axial ligands.
  • The observed invariance in reduction potentials suggests complex electronic interplay within these systems.
  • EPR studies provide insights into the electronic localization upon oxidation, differentiating between corrole and metal-centered processes.